Low energy process to produce a hydrophobic oil from biomass pyrolysis liquids

ABSTRACT

Described is a novel process for fractionating biomass pyrolysis oil quantitatively into energy dense hydrophobic aromatic fraction and water-soluble organics in an economical and energy efficient manner. Using the concepts of solvents and anti-solvent behaviors to separate the pyrolysis oil, which is an emulsion, a method utilizing minimal quantities of solvents and water is proposed, by comparison with the existing methods to isolate the hydrophobic aromatic fraction, there is a volume reduction of greater than 50:1. Additionally, there is a significant time saving over the 24 hours for the accepted method as a solvent, and the anti-solvent system is spontaneous.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the priority and benefit under 35 U.S.C. § 120to U.S. application Ser. No. 16/319,469 filed Jan. 21, 2019, titled “ALOW ENERGY PROCESS TO PRODUCE A HYDROPHOBIC OIL FROM BIOMASS PYROLYSISLIQUIDS”; which claims the priority and benefit under 35 U.S.C. § 120 toPCT Application No. PCT/GB2017/052147 filed Jun. 21, 2017 titled “A LOWENERGY PROCESS TO PRODUCE A HYDROPHOBIC OIL FROM BIOMASS PYROLYSISLIQUIDS”; which claims the priority and benefit under 35 U.S.C. § 120 toGB Application No. 1612716.9 filed Jul. 22, 2016, titled “A LOW ENERGYPROCESS TO PRODUCE A HYDROPHOBIC OIL FROM BIOMASS PYROLYSIS LIQUIDS”;the entirety of each and together are hereby expressly incorporated byreference as if fully set forth herein.

FIELD OF THE INVENTION

The present invention relates to a novel process for fractionatingbiomass pyrolysis oil quantitatively into energy dense hydrophobicaromatic fraction and water-soluble organics in an economical and energyefficient manner. Subsequent utilisation of these phases to is as rawmaterial precursors for the production of fuel range hydrocarbons, fueloils, fuel additives, fuel blends, concentrated fermentable sugars,industrial solvents, and chemicals.

BACKGROUND OF INVENTION

In recent years, thermochemical utilisation of biomass in the energysector has attracted renewed interest worldwide. The reason being, whilethe output of the other renewable energy sources is primarilyelectricity, biomass is able to produce liquid, gaseous, or solids ofvariable energy contents that can be used for energy or chemicalsproduction. Pyrolysis oil (PO) is a free-flowing liquid product producedfrom biomass fast pyrolysis. In the fast pyrolysis process, biomass israpidly heated to 450-550° C. in the absence of oxygen, with shortresidence time and quickly quenched to produce a condensate, which isknown as PO, bio-oil or bio-crude. Depending on the process conditionsand the condensation train, PO can be either a single-phase or atwo-phase mixture comprising a heavy viscous fraction and an aqueous lowviscosity fraction with light organic molecules. PO has been recognizedas a renewable feedstock for the production of transportation fuels andvarious other green applications.

PO as a fuel has many environmental advantages when compared to fossilfuels. Upon combustion, PO produces half of the NO_(x), negligiblequantities of SOX emissions when compared with fossil fuels, and is CO₂neutral. However, the large-scale production of liquid fuels from PO hasso far been limited because of its high acidity and thermal instability.Furthermore, PO has high water content (25-30%), high oxygen content(40-50%), is immiscible with fossil fuels, and undergoes phaseseparation and an increase in viscosity during prolonged storage(ageing).

PO is a complex mixture containing various kinds of oxygen-containingorganics (e.g. acids, aldehydes, alcohols, phenols, phenolicderivatives, sugars, and others with multiple functional groups). Theseoxygen-containing organic compounds make PO unstable, corrosive, andincompatible with conventional fuel and directly affect its commercialapplications. Therefore, it is necessary to upgrade the raw PO before itcan be used as a viable renewable fuel. Currently, there are nocommercial technologies that will produce fungible renewable fuels fromPO. Novel technologies need to be developed that can generate sufficientrenewable fuel volumes to replace or to blend with the current petroleumsources. Therefore, new methods and processes for upgrading PO arerequired.

Some PO upgrading technologies have been proposed to improve the productproperties and to increase the range of possible applications. Majorupgrading technologies include hydrodeoxygenation (HDO) andhydrocracking. Hydrogen consumption is very high for both thesetechnologies, which in turn affects the scale up and economics of theprocesses. It has become customary to practice the hydroprocessing of POby utilising a 2-stage approach in which the 1st stage comprises ahydrotreating stage utilising a mild temperature (<300° C.) for thereaction. This 1st stage reduces the polymerization of PO that occurswhen raw PO is subjected to temperatures >100° C. Hydrocracking thelightly hydrotreated product is then practised in a 2nd stage reactionat a higher temperature (>350° C.). The 2 stage hydroprocessing methodusually requires two reactors which increase the capital cost of thehydroprocessing technology; more reaction time is also requiredincreasing variable costs. Even without the considerations of highhydrogen consumption, these technologies face major challenges regardingcorrosion, catalyst fouling, catalyst stability and product selectivity.

Alternatively, some studies have been reported dealing with the chemicalupgrading of PO by esterification reaction with alcohol at mildconditions using mineral acid catalysts e.g. sulphuric acid, or variousheterogeneous catalysts including resin acid catalysts. From a chemicalpoint of view, it is anticipated that the organic acids and aldehydesare converted by the reactions with alcohols to esters and acetals,respectively. The product from the process mentioned above withdifferent catalysts still contains a high amount of water, ha lowcalorific value and large amounts of alcohol. The undesirable propertiesof PO are correlated with particular types of compounds. Acidscontribute to the corrosiveness of PO, and the instability of PO ismainly caused by the aldehydes, furans, ketones and phenols. Hence theseshould be suppressed in the final product. Also, pyrolytic sugars arepresent ˜14-33% mass ratio in many POs depending on the feedstock, andprocess conditions.

Oxygenates with furanic rings are most likely to form coke withaldehydes because of their thermal reactivity. These precursors react onthe catalytic surfaces and fill up the pores, which contributes toinactivation of catalysts during the upgrading and hydrodeoxygenationprocess of PO. Small aldehyde molecules are easily condensed togetherwith aromatics to form polymers. Although increasing the hydrogenpressure and reaction temperature while reducing the acidity of thecatalyst can drive down coking on the catalyst surface, it is asignificant challenge to minimise the hydrogen consumption and coking atmild conditions.

Effective separation of pyrolytic sugars and phenolic oligomers offersan array of industrial opportunities and also improves the quality ofthe PO for further processing. Pyrolytic-sugars can be useful for directupgrading to liquid transportation fuels and/or fermentation tocorresponding alcohols. Successful pyrolytic-sugars separation/removalalso has the potential for pharmaceutical applications. Phenolicoligomers have the ability to be used in various applications thatinclude resins, binders, asphalt, coatings, adhesives, aromaticchemicals, unique polymers, production of fuels and preservatives.

Currently, most of the PO phase separation processes involve eitheradding a large excess of water (Lindfors et al. 2014)(Bennett, Helle,and Duff 2009)(Vitasari, Meindersma, and de Haan 2011), typically a 10:1mass ratio to the PO or adding various quantities of aqueous saltsolutions to the PO(Song et al. 2009)(Fele Žilnik and Jazbinšek 2012).Also, by using salt solution the resultant product is contaminated withinorganic salts and a further washing step is required to remove theinorganic salts. Very high water requirement and the resultantwastewater treatment are other major disadvantages. Solvent/anti-solventphenomena have also been utilised using water and immiscible solventssuch as dichloromethane (Li, Xia, and Ma 2016). However, they have usedvery high quantities of anti-solvent i.e. almost equal to the amount ofpyrolysis oil. Also, considering the hazardous nature of the antisolvent(dichloromethane) and the amounts used are not economical for industrialscale-up. All these procedures require a minimum of 10 to 24 hh for thephase separation, and the resultant phase separated product is heavierand difficult to separate.

SUMMARY OF THE INVENTION

According to the invention, there is provided a process forquantitatively fractionating pyrolysis oil (PO) to produce twofractions, A) a hydrophobic aromatic fraction (HAF) and B) aconcentrated aqueous solution of water soluble organics; said processusing solvent/anti-solvent concepts and comprising the steps of;

a) the addition of an appropriate quantity of anti-solvent to the singlephase PO,

b) followed by addition of a specific volume of a solvent with mixing,

c) settling the mixture to allow phase separation into two fractions,thereby obtaining,

d) an organic phase comprising the solvent, the HAF and,

e) an aqueous phase comprising primarily the carbohydrate derived fromthe PO, along with acids, and low molecular weight phenolics.

Preferably, in step a), the anti-solvent is water or a mixture of waterwith low molecular weight alcohols to facilitate recovery of materials.Further preferably, the amount of antisolvent depending on the watercontent of the PO is in the range of 1-20% mass ratio concerning PO. Yetfurther preferably, the range is from 5 to 10% concerning pyrolysis oil.

Optionally, in step b) the solvent has a low solubility in water andpreferably a density of less than 1000 kg/m3 to obtain a densitydifference with the final water phase wherein the solvent phase/HAF isthe top phase and the water soluble are the bottom phases. Furtheroptionally, the solvent has less than 10% mass fraction solubility inwater and has a moderate polarity such that the solvent has an affinityfor the HAF. Still further optionally, the solvent forms an azeotropewith water when distilled. This allows different phases to be separatedmore easily.

Preferably, the solvent is selected from C₄-C₈ monohydric alcohols,C₂-C₈ alcohol esters and diethyl ether or mixture thereof. Furtherpreferably, the solvent is butyl acetate or a derivative of butylacetate.

The solvent is preferably present at from 1-20% mass ratio of the PO,and further preferably at from 5-10% mass ratio of the PO.

Preferably, the fractionation is carried out at a temperature in therange of from 15° C. to 75° C. Further preferably, the fractionation iscarried out at a temperature in the range of from 15° C. to 25° C. toreduce energy consumption.

Conveniently, in the hydrophobic aromatic fraction there is a volumereduction of greater than 50:1, allowing processing to be carried outmore easily and reducing Equipment costs.

Preferably, the fractionation is carried out in a continuous, or batchreactor systems.

Preferably, the fractionation time under normal gravity ranges from 15minutes to 2 hours.

Optionally, fractionation is carried out using centrifugal separation ata force in the range of from 8000 g-12000 g to accelerate and improveseparation.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 . Anti-solvent/solvent behaviour with pyrolysis oil (Winson typeemulsion).

FIG. 2 . Process of flow diagram to produce HAF.

FIG. 3 . Process of flow diagram to produce HAF with low molecularweight phenolics.

FIG. 4 . FTIR spectral comparison of HAF and pyrolignin.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a process for converting PO obtained bypyrolysis of biomass into high-quality fuel/boiler fuel/marine fuel,chemicals and fuel blends, pyrolytic sugars, phenolic oligomers andalkyl esters. In certain embodiments, a process is disclosed forfractionating or phase separating the PO and subsequently thesefractions will be used to produce specific high-value products, theprocess comprising steps in which, a) the organic phase of the phaseseparated product is further distilled to recover the solvent as well ashydrophobic aromatic polymer (HAF) as the primary product, and b) theaqueous phase of the phase separated product after a phase separationprocess is further processed by liquid-liquid extraction with solventsto extract and recover pyrolytic sugars and low molecular weightphenolics.

PO is a single-phase material as defined in ASTM D7544-12 StandardSpecification for Pyrolysis Liquid Biofuel—Grades G and Grade D. Thissingle-phase material has a low viscosity on the account of −25% massfraction of water embodied in what is recognised to be an emulsion. Theremainder of the material consists of water soluble smallmolecules—including acetic acid (HAc) as the most prominent; sugar andsugar polymers derived from the cellulose, and a hydrophobic aromaticpolymer (HAF) derived from both the lignin and the cellulose breakdown.Often the HAF is described as “pyrolytic lignin”, which is a term of artthat describes the substance that precipitates out of cold water when POis slowly added.

There is an analytical procedure to quantify the “pyrolytic lignin”wherein the PO is first mixed with an equal mass of water to obtain araw precipitate. This precipitate typically has about 50% of the initialmass. However, this is still contaminated with other materials from thePO and has to be re-dissolved in an equal mass of methanol. To thismixture, another equal mass e.g. 1 kg of water is added to precipitate apurified pyrolytic lignin from which the methanol has to be evaporated.

Alternative means of obtaining pyrolytic lignin make extensive use oforganic solvents. Again, the mass ratios of PO to solvent are at least1:1, and on separation, the solvent has to be water washed typicallyagain with an equal or greater mass, followed by an acid-base process toextract the HAF comprised of phenols and neutrals. Both of thesebehaviours are very characteristic of emulsions and breaking them intoseparate phases.

There is direct evidence for the emulsion nature of PO that has comefrom small angle neutron scattering (SANS). The main phase consists ofaggregates of lignin-derived molecules—while the dispersed phase is notvisible in SANS and is presumed to be the water and water solublemolecules. With ageing, the aggregates tend to grow, and they aretypically the equivalent volume of 4-coniferyl alcohol C-9 lignin units(typically called G-Lignin as they have the guiacyl OH and methoxysubstituents in the ring). The molecular weight of 4G-lignins i.e.tetramer lignin is approximately 700-750 g/mol.

As PO ages, there are chemical reactions taking place that result in theproduction of water, some cross-linking of small molecules, andaccording to the SANS results in agglomeration of the tetramer unitsinto larger units. This is not polymerization per se, the forces holdingthe tetramers together are van der Waals/Electrostatic, but the netresult is that these aggregates fall out of solution.

The VTT group has recently published further insight into the emulsionnature of single phase PO (Lehto et al. 2013). The picture that hasemerged is that the water insoluble (WIS) material—aka pyrolyticlignin—is held together using co-solvent molecules, in a loose networkwhich solubilizes the water, and water solubles. The co-solventmolecules are C1-C6 type small organic molecules with a polar group e.g.—OH (alcohol and phenol), >C═O, —COOH, and a non-polar hydrocarbon oraromatic “body”. The water soluble (WS) phase holds most of the water,and the organic molecules that are highly polar e.g. sugars includinganhydrosugars such as levoglucosan, and polyols e.g. sugar monomers andoligomers.

This emulsion can be destabilised by increasing the water to organicratio so that the WIS (tetramer lignin) separates, and then adding aco-solvent back to the freshly phase separated material such that asingle uniform phase is formed.

This is anti-solvent behaviour and the single-phase PO exists as a TypeIV Winsor emulsion as shown in FIG. 1 . In this case, the HAF (pyrolyticlignin) is behaving as a surfactant as well as an oil normallyimmiscible in water, while the polar organics are in an aqueoussolution. On increasing the water concentration the WIS (water insolubleHAF) forms a bottom phase on account of its density, and an upper phaseof mainly water and water soluble polar materials—a Winsor Type IIemulsion is created, and as shown in (Oasmaa et al. 2015), adding smallquantities of amphiphile molecules can reverse this and convert theWinsor Type II emulsion back to the apparent single phase Winsor Type IVemulsion.

There is, however, another Winsor emulsion—a type I which can be createdby adding a lipophilic polar solvent—one which has Hansen solubilityparameters in the range (Dispersion 8-10 MPa{circumflex over ( )}0.5,Polar 2-3 MPa{circumflex over ( )}0.5, and Hydrogen Bonding in the rangeof 2-4.5 MPa{circumflex over ( )}0.5). For a list of typical values fororganic molecules see (Hansen 2007). Only a small amount of thelipophilic polar solvent is needed if the Winsor type IV emulsion isclose to the critical point of converting to a Winsor type I emulsion.Then only a small amount of additional water as anti-solvent willtrigger the formation of the Type I emulsion with an aqueous phasecontaining the majority of the sugar and water-soluble organics, and asolvent phase containing the HAF—pyrolytic lignin.

For recovery of the HAF, the very concentrated solution in thelipophilic polar solvent can be extracted from a minuscule volume ofdistilled water, and after drying the solvent phase, the residual heavyoil can be recovered by evaporation of the solvent. The combined waterphase can be extracted with organic solvents and subsequently distilledto produce clean fractions of pyrolytic sugars and phenolic monomers.Further, these phenolic monomers can be added back to the HAF fractionfor the future upgrading purposes.

Using the Winsor emulsion behaviour, the additional volumes of solventand water are minimized. Process flow diagram of the process is shown inFIGS. 2 and 3 . In FIG. 2 , to the PO (10), solvent (20) is added atfirst and stirred vigorously for ˜30 minutes at room temperature in abatch or continuous reactor (100). Wherein the amount of solvent,depending on the water content of the PO is in the range of 1-20% massratio concerning PO. Wherein the preferable is range is from 5 to 10%concerning the PO.

To this mixture, solvent (30) is added and stirred vigorously for ˜60minutes at room temperature in a batch or continuous reactor (200). Thesolvents are selected from C₄-C₈ monohydric alcohols, C₂-C₈ alcoholesters and diethyl ether. The preferable solvents are butyl acetate andany derivatives of butyl acetate. The amount of solvent added is,dependent on the water content of the PO, and is in the range of 1-20%mass ratio concerning PO. Wherein the preferable is range is from 5 to10% concerning the PO.

After settling the mixture for about 10 to 90 minutes, a clear, distinctphase separation is achieved i.e. a top organic phase (300) and a bottomaqueous phase (400). Further distillation (301) of the top organic phase(300) results in HAF (700) and also anti-solvent (20R) and solvent (30R)which are recycled. The bottom aqueous phase (400) is further solventextracted followed by distillation to produced pyrolytic sugars (500)and phenolic monomers (600).

The process shown in FIG. 3 follows the same procedure as FIG. 2 butalso, the phenolic monomers (600) produced from the bottom aqueous phase(400) are added to the final HAF product (701). This addition, in turn,increases the yields of the HAF of up to 10%. Also, recycled solvent(30R1) and anti-solvent (20R1) from bottom aqueous phase are added backto the recycling lane.

In a typical example starting with 100% of PO the addition of butylacetate (˜10%), and 5˜2% of water anti-solvent concerning PO, willproduce an instant phase separation into the fractions of a top organicphase (42%) and bottom aqueous phase (58%). Assuming all the 100% butylacetate or solvent is recycled, the overall yields from the processcomprising of 36% of HAF, 30% of pyrolytic sugars, 11% phenolic monomersand the rest is residual water (˜23%). In most cases, these yields varybetween the type of feedstocks and processing conditions used to producethe corresponding PO. In another scenario, the 11% phenolic monomers areadded back to the HAF fraction, and this will increase the overall yieldof HAF to 47%. The fractionation step is typically carried out at atemperature of from 0° C.-75° C. However, a range of from 15-75° C. ispreferred and especially from 15-25° C. Although temperatures in therange of 0-15° C. produce faster fractionation, the shortened timeperiod is offset in cost and energy terms by the increased cost incooling the system.

The HAF produced from the above steps, and then evaporation of thesolvent produces a viscous black liquid with the same properties as thepyrolytic lignin isolated using water washing methods. This is alsoconfirmed by the FTIR spectral comparing of the HAF and pyrolignin asshown in FIG. 4 .

Eligible solvents are required to have Hansen parameters in the aboverange, and simultaneously must have low solubility in water, anddepending on the downstream process requirements, there will be a needfor appropriate stability, environment, health and safetycharacteristics to enable its recovery.

Analytical Methods

Viscosity

Viscometric measurements were performed at 40° C. with a BrookfieldDV-11+ Pro viscometer with small sample adapter and spindle SC4-18.

Heating Value Measurements

To determine the higher heating value (HHV) of the biofuels anddifferent phases, approximately 1 g of samples were burned in an IKAC5003 type bomb calorimeter under 3 MPa oxygen pressure and in thedynamic method of operation. Standardisation and thermochemicalcorrections followed the ASTM D 240 test method. Samples with high watercontent were combusted with paraffin strips as spiking material (45.78MJ/kg).

TAN and Water Analyses

The total acid number (TAN) and water content of the fuel samples weredetermined by Aqumax TAN and Aquamax KF Volumetric titrators(GRScientific) according to ASTM D 664 and ASTM E 203 standards.

CHN

The elemental composition analysis of the samples (C, H and N) wascarried out at 900° C. by a Flash 2000 analyser, and the oxygen content(O) was calculated by difference.

GC-MS Analysis

Sugar compounds were analysed by gas chromatography-mass spectrometry(Agilent 7890A GC-MS) after a standard trimethylsilylation with HMDS.The injection unit temperature of the GC was 300° C., and it was coupledto an HP-VOC column (60 m×0.2 mm, 1.12 μm). The GC oven was heated from45° C. to 280° C. at a rate of 3 K/min while the system was purged withhelium carrier gas with a split ratio of 25. Separated compounds wererecorded with the Agilent 5975C mass selective detector with ionisationenergy of 70 eV and a scanning range of m/z 30-550 in the full scanmode.

EXAMPLES Example 1

100 grams of PO was placed into a 500 cm3 autoclave equipped with amagnetic stirrer. To this approximately 2-10% mass ratio of anti-solvent(for ex. distilled water) was added with stirring (˜1000 rpm) at roomtemperature for the duration of 10-60 minutes. To the resultant product,1-30% mass ratio of solvent (for ex. butyl acetate) was added andstirred vigorously (˜1000 rpm) for the duration of 10-60 minutes. Afterleaving the mixture at ambient temperature, the liquid product consistedof two phases: a dark organic phase at the top and an aqueous phase atthe bottom. These phase-separated products were centrifuged to obtain aclean separation of the organic and aqueous phases. The organic phasewas subsequently distilled. Distillation yields a two-phase liquidproduct, a top light yellow organic phase (solvent) and a minor amountof colourless aqueous phase. The HAF will remain in the distillationflask. Similarly, the aqueous phase from an earlier phase separationprocess was put in a separatory funnel, and an equal amount of diethylether was slowly added, and the funnel was shaken vigorously for severalminutes and then allowed to rest for approximately 30 min. The resultantsolution separated into two distinct layers. The upper layer and bottomlayer were designated as ether-soluble (ES) fraction and the ethersinsoluble (EIS) fraction, respectively. Subsequently, from the ESfraction, ether was removed under reduced pressure with a rotaryevaporator resulting in a low molecular weight phenolics. For the secondliquid-liquid extraction, an equal quantity of dichloromethane was addedto the EIS fraction, and the mixture was shaken for several minutesbefore being allowed to sit for approximately 30 min. The mixturegradually separated into two layers. The bottom layer was designated asthe dichloromethane-soluble fraction of EIS (DCMS), and the upper layerwas the dichloromethane-insoluble fraction of the EIS (DCMIS). Thelayers were separated, and the dichloromethane was removed under thevacuum with a rotary evaporator. Subsequent distillation of the DCMISfraction yields a high amount of pyrolytic sugars and water as aby-product. Also, a subsequent distillation of both the ES fraction andDCMS fraction yields a high amount of low molecular weight phenolics andsolvent as a by-product, and it will be further recycled to use forextraction purposes.

The typical product yields from this process are HAF (35-50% massratio), pyrolytic sugars (20-30% mass ratio), phenolics (8-12% massratio) and the remainder is the water content. These yields mostlydepend on the type of biomass feed used to produce the PO and varybetween feed to feed. Table 1 shows the comparison of properties ofcrude PO and HAF such as viscosity, HHV, Total acid number (TAN), watercontent and elemental analysis.

TABLE 1 Comparison of physical and chemical properties of crude PO,pyrolignin, HAF and HAF with phenolics Pyrolysis HAF with Property oilPyrolignin HAF phenolics Units Total acid 111.85 73 88.15 103 mgKOH/gnumber Water mass 23 3 1.60 2.7 % fraction Density 1.12 na 1.15 na g/cm³C mass fraction 41.68 55.95 62.61 60.42 % H mass fraction 7.61 7.26 7.406.98 % O mass fraction 50.70 36.80 29.99 32.60 % (by difference)Viscosity 22.60 na 268 na mPa · s at 40° High heating 18.3 24.37 28.0026.03 MJ/kg value, dry basis

Example 2

100 grams of PO was placed into a 500 cm³ autoclave equipped with amagnetic stirrer. To this approximately 2-10% mass ratio of anti-solvent(for example distilled water) was added with stirring (˜1000 rpm) atroom temperature for the duration of 10-60 minutes. To the resultantproduct, 1-30% mass ratio of solvent (for example butyl acetate) wasadded and stirred vigorously (˜1000 rpm) for 10-60 minutes. Afterleaving the mixture at ambient temperature, the liquid product consistedof two phases: a dark organic phase at the top and an aqueous phase atthe bottom. These phases separated products were centrifuged to obtain aclean separation of the organic and aqueous phases. It has been foundthat a preferred range for the centrifugation step is at an appliedforce of 8000 g-12000 g.

The aqueous phase from the above phase separation process was put in aseparatory funnel, and an equal amount of butyl acetate was slowlyadded, and the funnel was shaken vigorously for several minutes beforebeing allowed to rest for approximately 30 min. The resultant solutionseparated into two distinct layers. The upper layer and bottom layerwere designated as a butyl acetate-soluble (BS-1) fraction and the butylacetate-insoluble (BIS-1) fraction, respectively. Subsequently, an equalquantity of butyl acetate was slowly added to the BS-1 fraction, and thefunnel shaken vigorously for several minutes and then allowed to restfor approximately 30 min. The resultant solution separated into twodistinct layers. The upper layer and bottom layer were designated as abutyl acetate-soluble (BS-2) fraction and the butyl acetate-insoluble(BIS-2) fraction, respectively. The fractions BS-1 and BS-2 werecombined and added to the dark organic phase obtained from the firstphase separation of PO. Finally, the resultant mixture (a dark organicphase+BS-1 &2) was subjected to distillation under vacuum or atmosphericconditions to remove or evaporate the butyl acetate and water. The HAFremained in the distillation flask. Similarly, a subsequent distillationof the BIS-2 fraction yielded a high amount of pyrolytic sugars andwater as a by-product.

The typical product yields from this process are HAF (35-50% massratio), pyrolytic sugars (20-30% mass ratio), with the remainder isbeing water content. These yields mostly depend on the type of biomassfeed used to produce the PO and vary from feed to feed. Table 2 showsthe comparison of properties of crude PO and HAF such as viscosity, HHV,Total acid s number (TAN), water content and elemental analysis.

TABLE 2 Comparison of physical and chemical properties of crude PO,pyrolignin, and HAF with phenolics Pyrolysis HAF with Property oilPyrolignin phenolics Units Total acid 111.85 73 85 mgKOH/g number Watermass 23 3 0 % fraction Density 1.12 na 1.18 g/cm³ C mass fraction 41.6855.95 64.0 % H mass fraction 7.61 7.26 6.80 % O mass fraction 50.7036.80 29.20 % (by difference) Viscosity 22.60 na na mPa · s at 40° Highheating 18.3 24.37 27.4 MJ/kg value, dry basis

1-18. (canceled)
 19. A process comprising: fractionating pyrolysis oilto yield: an organic phase comprising hydrophobic aromatics, and anaqueous phase comprising water soluble organics; and extracting theaqueous phase with an organic solvent to yield: a fraction that issoluble in the organic solvent, and a fraction that is insoluble in theorganic solvent.
 20. The process according to claim 19, wherein theextracting comprises: combining the aqueous phase and the organicsolvent to yield a mixture; agitating the mixture; and allowing themixture to settle.
 21. The process according to claim 19, furthercomprising distilling the fraction that is soluble in the organicsolvent to remove the organic solvent, thereby yielding a product. 22.The process according to claim 21, wherein the product comprisesphenolic monomers.
 23. The process according to claim 19, furthercomprising: extracting the fraction that is insoluble in the organicsolvent with an additional organic solvent to yield: a fraction that issoluble in the additional organic solvent, and a fraction that isinsoluble in the additional organic solvent.
 24. The process accordingto claim 23, further comprising distilling the fraction that isinsoluble in the additional organic solvent to remove water, therebyyielding a product.
 25. The process according to claim 23, wherein theproduct comprises pyrolytic sugars.
 26. The process according to claim23, further comprising removing the additional organic solvent from thefraction that is soluble in the additional organic solvent.
 27. Theprocess according to claim 23, further comprising: combining thefraction that is soluble in the organic solvent and the fraction that issoluble in the additional organic solvent to yield a mixture.
 28. Theprocess according to claim 27, further comprising distilling the mixtureto remove the organic solvent and the additional organic solvent,thereby yielding a product.
 29. The process according to claim 28,wherein the product comprises phenolics.
 30. The process according toclaim 23, further comprising: combining the fraction that is soluble inthe organic solvent, the fraction that is soluble in the additionalorganic solvent, and the organic phase to yield a mixture.
 31. Theprocess according to claim 30, further comprising distilling the mixtureto remove the organic solvent, the additional organic solvent, and waterthereby yielding a product.
 32. The process according to claim 31,wherein the product comprises the hydrophobic aromatics.
 33. The processaccording to claim 23, wherein extracting the fraction that is insolublein the organic solvent with the additional organic solvent comprises:combining the fraction that is insoluble in the organic solvent and theadditional organic solvent to yield a mixture; and allowing the mixtureto settle.
 34. The process according to claim 19, wherein the organicsolvent is diethyl ether.
 35. The process according to claim 34, whereinthe additional organic solvent is dichloromethane.
 36. The processaccording to claim 19, wherein the organic solvent is butyl acetate. 37.The process according to claim 36, wherein the additional organicsolvent is butyl acetate.
 38. A process comprising: fractionatingpyrolysis oil to yield: an organic phase comprising hydrophobicaromatics, and an aqueous phase comprising water soluble organics;extracting the aqueous phase with diethyl ether to yield: a diethylether-soluble fraction, and a diethyl ether-insoluble fraction;extracting the diethyl ether-insoluble fraction with dichloromethane toyield: a dichloromethane-soluble fraction, and adichloromethane-insoluble fraction; distilling thedichloromethane-insoluble fraction to remove water, thereby yieldingpyrolytic sugars; distilling the diethyl ether-soluble fraction and thedichloromethane-soluble fraction to remove the diethyl ether and thedichloromethane, thereby yielding phenolic monomers.
 39. A processcomprising: fractionating pyrolysis oil to yield: an organic phasecomprising hydrophobic aromatics, and an aqueous phase comprising watersoluble organics; extracting the aqueous phase with butyl acetate toyield: a first butyl acetate-soluble fraction, and a first butylacetate-insoluble fraction; extracting the first butyl acetate-insolublefraction with additional butyl acetate to yield: a second butylacetate-soluble fraction, and a second butyl acetate-insoluble fraction;distilling the second butyl acetate-soluble fraction to remove water,thereby yielding pyrolytic sugars; combining the first butylacetate-soluble fraction and the second butyl acetate-soluble fractionwith the organic phase to yield a mixture; and distilling the mixture toremove the butyl acetate and water, thereby yielding the hydrophobicaromatics.